M.Sc. Chemistry First Year 2012-13

M.Sc. Chemistry First Year 2012-13 (Each Semester of 15 weeks) For Affiliated Colleges Total pds. 45 minutes I SEMESTER: Four theory courses Paper I CH 401 Inorganic Chemistry Paper II CH 403 Organic Chemistry Paper III CH 405 Physical Chemistry Paper IV CH 407 Analytical Chemistry

90 90 90 90 _________ 360

PRACTICALS: 4 pds/ day

24 pds./ week

CH 409 Inorganic Chemistry CH 410 Physical Chemistry

360 pds./ semester

4 day/week 2 day/week

II SEMESTER: Four theory courses Paper I CH 402 Inorganic Chemistry Paper II CH 404 Organic Chemistry Paper III CH 406 Physical Chemistry Paper IV CH 408 Analytical Chemistry

90 90 90 90 _____ 360

PRACTICALS: 4 pds/ day CH 411 Organic Chemistry CH 412 Physical Chemistry

24 pds./ week … …

360 pds./ semester

4 days/week 2 days/week

EXAMINATION SCHEME: I SEMESTER: FOUR THEORY PAPERS CH 401 CH 403 CH 405 CH 407

3 Hrs. 50 marks 3 Hrs. 50 marks 3 Hrs. 50 marks 3 Hrs. 50 marks _____________ 200

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PRACTICAL EXAMINATIONS: (A) Inorganic Chemistry (B) Physical Chemistry Total II SEMESTER:

12 Hrs. (2 days) 6 Hrs. (1 day)

67 marks 33 marks 100

FOUR THEORY PAPERS: CH 402 CH 404 CH 406 CH 408

3 Hrs. 50 marks 3 Hrs. 50 marks 3 Hrs. 50 marks 3 Hrs. 50 marks _____________ 200

PRACTICAL EXAMINATIONS: (A) Organic Chemistry 12 Hrs. (2 days) 66 marks (B) Physical Chemistry 6 Hrs. (1 day) 34 marks Total 100 -----------------------Total marks of M.Sc. Previous: 600 M.Sc. (Final) Chemistry (2013-14):(Each Semester of 15 weeks) III Semester: Paper I Paper II Paper III Paper IV

CH 501 Spectroscopy CH 502 Photochemistry & Solid State Chemistry CH 503 Environmental Chemistry CH 504 Biochemistry

Practicals

4 pds.

24 pds./week

Total pds. of 45 minutes 90 90 90 90 _________________ 360 periods 360 pds./semester

There will be 2 Lab curses. Students will work for 7 weeks each in lab 1 and 2 CH 511 CH 512

Lab. Course 1 (Inorganic) Lab. Course 2 (Analytical)

IV SEMESTER A student will opt for any one of the four elective groups. Elective Group A C. No. 601/602/603/604 90 Elective Group B C.No.611/612/613/614 90 Elective Group C C.No.621/622/623/624 90 Elective Group D C.No.631/632/633/634 90 __________ 360 periods 2

Practicals

4 pds./day

24 pds./week

360 pds./semester

There will be 2 Lab curses. Students will work for 7 weeks each in Lab 3 and Lab 4 in IV sem . CH 513 CH 514

Lab. Course 3 (Organic) Lab. Course 4 (Physical)

Examination Scheme M.Sc. III Semester: 4 theory papers of: CH 501 CH 502 CH 503 CH 504

3 Hrs. 3 Hrs. 3 Hrs. 3 Hrs.

Practical examinations: (a) Lab. 1 6 Hrs. 50 marks

50 marks 50 marks 50 marks 50 marks

200 marks

12 Hrs. (2 days)

100 marks.

Lab.2 6 Hrs. 50 marks

IV Semester: 4 Theory papers (Elective) Practical examinations:

50 marks

total

12 Hrs. (2 days)

Lab. 3

Lab. 4

6 Hrs. 50 marks

6 Hrs. 50 marks

Total Marks of M.Sc. (F)

200 marks. 100 marks.

--------------------600

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M.Sc. I YEAR-2012-13 SEMESTER – I

CH 401 INORGANIC CHEMISTRY: UNIT I Stereochemistry and bonding in main group compounds. VSEPR, Walsh diagrams of tri -atomic molecules, dπ-pπ bonds, Bent rule and energetics of hybridization, some simple reactions of covalently bonded molecules.

UNIT II Metal Ligand Bonding. Limitation of crystal field theory, molecular orbital theory, octahedral, tetrahedral and square planer complexes, π-bonding and molecular orbital theory. Comparision with CFT

UNIT III Metal Ligand Equilibria in solution stepwise and overall formation constants and their interaction, trends in stepwise constants, factors affecting the stability of metal complexes with reference to the nature of metal ion and ligand, chelate effect and its thermodynamic origin, determination of binary formation constants by pH metry and spectrophotometry.

UNIT IV Correlation diagrams of Transition Metal Complexes. Spectroscopic ground states, correlation, Orgel and Tanabe Sugano diagrams for transition metal complexes (d1to d9 states), calculation of Dq, B and β parameters.

UNIT V Electronic Spectra and Magnetic properties of Transition Metal Complexes. Charge transfer spectra, spectroscopic method of assignment of absolute configuration in optically active metal chelates and their stereochemical information, anomalous magnetic moments, magnetic exchange coupling and spin crossover.

Books Suggested: 1. 2. 3. 4. 5. 6.

Advanced Inorganic Chemistry, F.A. Cotton and Wilkinson, John Wiley. Inorganic Chemistry, J.E. Huhey, Harpes & Row. Chemistry of the Elements, N.N. greenwood and A.Earnshow, Pergamon. Inorganic Electronic Spectroscopy, A.B.P. lever, Elsevier. Magnetochemistry, R.L.Carlin, Springer Verlag. Comprehensive Coordination Chemistry eds., G. Wilkinson, R.D. Gillars and LA McCleverty, Pergamon.

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CH 403 ORGANIC CHEMISTRY UNIT I Nature of Bonding in Organic Molecules Delocalized chemical bonding-conjugation, cross conjugation, reasonance hyperconjugation, bonding in fullerenes, tautromerism. Aromaticity in benzenoid and non-benzenoid compounds, alternant and non-alternant hydrocarbvonds, Huckel’s rule, energy level of π-molecular orbitals, annulenes aromaticity, homo-aromaticity, PMO (approach). Bonds weaker than covalent- addition conmpounds, crown ether complexes anc cryptand inclusion compounds, cyclodextrins, catenanes and rotaxanes.

UNIT II Stereochemistry I Conformational analysis of cycloalkanes, decalins, effect of conformation on reactivity conformation of sugars, steric strain due to unavoidable crowding. Stereochemistry of the compounds containing nitrogen, sulphur and phosphorus. UNIT III

Stereochemistry II Elements of symmetry, chirality, molecules with more than one chiral center, threo and erythro isomers, methods of resolution, optical purity, enantiotopic and diastereotop atoms, groups and faces, stereospecific and stereoselective synthesis. Asymmetric synthesis. Optical activity in the absence of chiral crbon (biphenyls, allenes at spiranes), chirality due to helical shape.

UNIT IV Reaction Mechanism: Structure and Reactivity Types of mechanisms, types of reactions, thermodynamic and kinetic requirements, Kinetic and thermodynamic control. Hammond’s postulate, Curtin-Hammett principle, Potential energy diagrams, transition states and intermediates, methods of determining mechanism isotope effects. Hard and osft acids and bases. Generation, structure, stability and reactivity of carbocations, carbanions free radicals, carbenes and nitrenes. Effect of structure on reactivity – resonance and field effects, steric effecgt, quantitative treatment. The Hammett equation and linear free energy relationship. substituent and reaction constants. Taft equation.

UNIT V

Pericyclic Reactions Molecular orbital symmetry, Frontier orbitals of ethylene, 1,3- butadiene, 1,3,5hexatriene and allyl system. Classification of pericycle reactions. Woodward – Hoffmann correlation diagrams, FMO and PMO approach. Electrocyclic reactions – conrotatory and 5

disrotatory motions, 4n, 4n+2 systems, 2+2 addition of ketenes, 1,3 dipolar cycloadditions and cheleotropic reactions. Sigmatropic rearrangements – suprafacial and antarafacial shifts of H, sigmatropic shifts involving carbon moieties, 3,3- and 5,5- sigmatropic rearrangements. Claisen, Cope and aza-Cope rearrangements. Fluxional tautomerism. Ene reaction. Books Suggested: 1. Advanced Organic Chemistry-Reactions, Mechanism and Structure, Jerry March, John Wiley. 2. Advanced Organic Chemistry, F.A. Carey and R.J.Sundberg, Plenum. 3. A Guide Book to Mechanism in Organic Chemistry, Peter Sykes, Longman. 4. Structure and Mechanism in Organic Chemistry, C.K.Ingold, Cornell University Press. 5. Organic Chemistry, R.T. Morrison and R.N.Boyd, Prentice-Hall 6. Modern Organic Reactions, H.O. House, Benjamin. 7. Principles of Organic Synthesis, R.O.C. Norman and J.M. Coxon, Blackie Academic & Professional. 8. Pericyclic Reactions, S.M.Mukherji, Macmillan, India. 9. Reaction Mechanism in Organic Chemistry S.M.Mukherji and S.P. Singh, Macmillan. 10. Stereochemistry Organic Compounds, D.N.asipuri, New Age International. 11. Stereochemistry of Organic Compounds, P.S.Kalsi, New Age Internationa. 12. Pericyclic Reactions by Jagdama Singh.

CH 405 PHYSICAL CHEMISTRY UNIT I Chemical Dynamics: Ionic reactions, kinetic salt effects, steady state kinetics, kinetic and thermodynamic control of reactions. Dynamic chain (hydrogen-bromine reaction, pyrolysis of acetaldehyde). photochemical (hydrogen-bromine and hydrogen-chlorine reactions) and oscillagtory reactions (Belousov Zhabotinsky reaction).

UNIT II Homogeneous and heterogeneous catalysis, kinetics of enzyme reactions, general features of fast reactions, study of fast reactions by flow method, relaxation method, and flash photolysis method. Dynamics of molecular motions, probing the transition state, dynamics of barrierless chemical reactions in solution, dynamics of unimolecular reaction, Lindemann and Hinshelweed theories of unimolelcular reactions.

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UNIT III Adsorption Surface tension, capillary action, pressure difference across curved surface (Laplace equation), vapour pressure of droplets (Kelvin equation) Gibbs adsorption isotherm, estimation of surface area (BET equation), surface films on liquids Electro-kinetic phenomenon and quantitative treatment of Zeeta potential.

Micelles Surface active agents, classification of surface active agents, micellization, hydrophotic interaction, critical micellar concentration (CMC), factors affecting the CMC of surfactants, counter ion binding to micelles, UNIT IV

Mecromolecules Polymer – definition, types of polymers, electrically conducting, fire resistant, liquid crystal polymers, kinetic of polymerization, mechanism of plymerization. Molecular mass, numjber and mass average molecular mass, molecular mass determination (osmometry, viscometry, deiffusion and light scattering methods), sedimention, chain configuration of macromelecules, calculation of average dimensions of various chain structures. UNIT V Electrochemistry Electrochemistry of solutions. Debye-Huckel – Onsagar treatment and its extension, Debye-Huckel-Jerrum mode, ion - solvent interactions, Born model. Thermodynamics of electrified interface; Derivation of electrocapillary Lippmann equation (surface excess), Structure of electrified interfaces. Helmholtz, Guoy-Chapman and Stern models. Over potentials, exchange current density, Butler – Volmer equation, Tafel plot. Introduction to corrosion, theories, forms of corrosion, corrosion monitoring and prevention methods.

Books Suggested : 1. Physical Chemistry, P.W. Atkins, ELBS. 2. Chemical Kinetics, K.J.Laidler, Megraw-Hill 3. Kinetics and Mechanism of Chemical Transformation, J.Rajaraman and J.Kuriacose, McMillan. 4. Micelles, Theoretical and Applied Aspects, V.Moroi, Plenum. 5. Modern Electrochemistry Vol. I and Vol. II, J.O.M. Bockris and A.K.N.Reddy, Plenum. 6. Introduction to Polymer Science, V.R.Gowarkar, N.V.Vishwananathan and J.Sridhar, Wiley Eastern.

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CH 407 ANALYTICAL CHEMISTRY: Unit I Fundamentals of Chemical Analysis Quantitative and Qualitative analysis; Sensitivity and Selectivity of Analytical methods; Sampling; Accuracy & precision; Standard Deviation; Calibration curve and Correlation Coefficient; linear regression;, student ‘t’ test, Analysis of Variance (ANOVA). Unit II Solvent extraction: Quantitative and Qualitative treatment of solvent extraction; Organic reagents dithiols, diketones, oxine, dithizone, cuproin, cupferron, dimethylglyoxime and dithiocarbamates in solvent extraction; Synergistic Extraction: determination of Nickel; Crown ethers for ion association complexes. Unit III Ion Exchange: Basic features of ion exchange reactions; Ion exchange resins and their classification; action of ion exchange resins; Factors affecting the selectivity of ion exchange resin; Ion Exchange capacity, Ion selective Electrodes. Unit IV Separation Techniques: Principle, methodology and applications: Super Critical Fluid Chromatography, Ion Exchange Chromatography, Gel Filtrations and Gel Permeation Techniques; Electrophoresis. Unit V Spectroscopic Techniques: Principle, General layout of instrument and applications of: Flame Photometry; Atomic Absorption Spectroscopy (AAS); Fluorescence Spectroscopy; Nephelometry & Turbidometry.

Books: 1. Vogel’s Textbook of Quantitative Chemical Analysis, G.H.Jeffery, J.Bassett, J. Mendham and R.C. Denney, Publ ELBS, Longman, UK 2. Basic Concepts of Analytical Chemistry, S. M. Khopkar, Wiely Eastern. 3. Fundamentals of Analytical Chemistry, D.A. Skoog, D.M. West and F.J.Holler. Publ. W B Saunders. 4. Analytical Chemistry, G.D. Christian, John Willy & Sons.

CH 409 Laboratory Course-I Inorganic Chemistry Qualitative and Quantitative Analysis. (a) Less common metal ions – TI, Mo, W, Ti, Zr, Th, V, U (two metal ions in cationic/anionic forms). (b) Insoluble – oxides, sulphates and halides. (c) Separation and determination of two metal ions Cu-Ni, Ni-Zn, Cu-Ag etc. involving volumetric and gravimetric methods. 8

Chromatography Separation of cations and anions by (a) Paper Chromatography (b) Column Chromatography – Ion exchange.

Preparations Preparation of selected inorganic compounds and their studies by I.R., eletronic Mossbauer, E.S.R. and magnetic susceptibility measurements. Handling of air and moisture sensitive compounds. (1) VO (aca)2 (2) TiO(C9H8NO)2 2H2O (3) Cis-K[Cr(C2O4)2(H2O)2] (4) Na[NH3)2(SCN)4] (5) Mn(acac)3 (6) K3[Fe(C2O4)3] (7) Prussian Blue, Turnubull’s Blue (8) [Co(NH3)6][Co(No2)6] (9) Cis-[Co(trine)(NO2)2]Cl.H2O (10) Hg[Co(SCN)4] (11) {Co(Py)2Cl2] (12) [Ni(NH3)6]Cl2 (13) Ni(dmg)2 (14) [Cu(NH3)4]SO4.H2O CH 410 Physical Chemistry

Error Analysis and Statistical Data Analysis Errors, types of errors, minimization of errors, error distribution curves, precision, accuracy and combination; statistical treatment for error analysis, student ‘t’ test, null hypothesis, rejection criteria F 7 Q test; linear regression analysis, curve fitting. Calibration of volumetric apparatus: burette, pipette and standard flask.

Chemical kinetics (i) (ii)

(iii) (iv)

To compare the strengths of HCl and H2SO4 by studying the kinetics of hydrolysis of an ester. Determination of the effect of (a) Change of temperature (b) Change of concentration of reactant and catalyst and (c) Ionic strength of the media on the velocity constant of an acid hydrolysis of an ester. Determination of the velocity constant of hydrolysis of an ester/ionic reaction in micellar media. Determination of the rate constant for the oxidation of iodide ions by hydrogen peroxide by studying the kinetics as an iodine clock reaction. 9

(v)

To study the effect of acid strength on the reaction of acetone and iodine.

Colorimeter (i) To test the validity of Beer-Lambert law using colorimeter/spectrophotometer and determination of the unknown concentration of a solution.

Surface Tension (i) (ii)

To determine the parachor of carbon and hydrogen atoms by drop weight method. To determine the relative efficiencies of different detergents by suface tension measurements.

Book Suggested: 1. Vogel’s Textbook of Quantitative Analysis, revised, J.Bassett, R.C. Denney, GH.H. Jeffery and J. mENDHAM, elbs. 2. Synthesis and Characterization of Inorganic Compounds, W.L.Jolly, Prentice Hall. 3. Experiments and Techniques in Organic Chemistry, D. Pasto, C.Johnson and M.Miller, Prentice Hall 4. Macroscale and Microscale Organic Experiments, K.L. Williamson, D.C. Heath. 5. Systematic Qualitative Organic Analysis, H. Middleton, Adward Arnold. 6. Handbook of Organic Analysis – Qualitative and Quantitative, H. Clark, Adward Arnold. 7. Vogel’s Textbook of Practical Organic Chemistry, John Wiley. 8. Practical Physical Chemistry, A.M.James and F.E. Prichard, Longman. 9. Findley’s Practical Physical Chemistry, B.P.Levitt, Longman. 10. Experimental Physical Chemistry, R.C.Das and B.Behera, Tata McGraw Hill. 11. Advanced Practical Physical Chemistry, J.B.Yadav, Goel Publishing House. 12. Advanced Experimental Chemistry, Vol. I – Physical, J.N.Gurtu and R.Kapoor, S.Chand & Co.

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M.Sc. I YEAR-2012-13 SEMESTER II CH 402 INORGANIC CHEMISTRY UNIT I Reaction mechanism of Transitions metal complexes: Energy profile of a reaction (transition state or activated complex) nucleophilic and electrophilic substitution, factors responsible for including SN1 and SN2 reaction, Lability and inertness of octahedral complexes acc to VBT and CFT. Acid hydrolysis, factor affecting acid hydrolysis, base hydrolysis, conjugate base mechanism (SN1 CB) Evidences in favour of conjugate base mechanism, anation reactions, Substitution reaction without metal-ligand bond cleavage (Special reference to Co(III) complexes).

UNIT II Substitution in square planer complexes: Transeffect, mechanism of substitution reaction, polarization theory and π bonding theory. Redox reaction : electron transfer reaction, mechanism of one electron transfer reaction, outer sphere reaction, Inner sphere reaction, bridge intermediate mechanism.

UNIT III Metal π-complexes: Metal carbonyls, structure and bonding in metal carbonyls, vibrational spectra of metal carbonyls for bonding and structural elucidation. Preparation, bonding, structure and important reactions of transition metal nitrosyl.

UNIT IV Boranes : Structure and bonding in diborane, preparations of higher Boranes, Lipscomb’s concept of bonding elements in higher Boranes.

UNIT V Metal clusters: Metal carbonyl and halide clusters, compounds with metal metal multiple bonds, metalloboranes. Books Suggested: 1. F.A. Cotton and Wilkinson: Advanced Inorganic Chemistry, John Wiley. 2. J.E. Huhey: Inorganic Chemistry, Harper and Row. 3. N.N.Green Wood and A. Eafnshow: Chemisry of the element, Pergamon. 4. A.B.P. Lever: Inorganic Electronic Spectroscopy, Elsevier 5. R.L.Carlin: Magnetochemistry, Verlag. 6. G. Wilkinson, R.D. Gillars and J.A. MCeLEVERTY: Comprehensive Coordination Chemistry eds. Pergamon. 7. F. Basolo and R.G. Pearson: Mechanism of Inorganic Reaction, Wiley Eastern. 11

CH 404 ORGANIC CHEMISTRY UNIT I

Aliphatic Nucleophilic Substitution The SN2, SN1, mixed SN1 and SN2 and SET mechanisms. The neighbouring group mechanism, neighbouring group participation by π and σ bonds, anchimeric assistance. Classical and nonclassical carbocations, phenonium ions, norbornyl system, common carbocation rearrangements. Application of NMR spectroscopy in the detection of carbocations. The SNi mechanism. Nucleophilic substitution at an allylic, aliphatic trigonal and a vinlyic carbon. Reactivity effects of substrate structure, attacking nucleophile, leaving group and reaction medium, phase transfer catalysis and ultrasound, ambident nucleophile, regioselectivity.

Aliphatic Electrophilic Substitution Bimolecular mechanisms- SE2 and SEi. The SE1 mechanism, electrophilic substitution accompanied by double shifts. Effect of substrates, leaving group and the solvent polarity on the reactivity.

UNIT II Aromatic Electrophilic Substitution The arenium ion mechanism, orientation and reactivity, energy profile diagrams. The ortho/para ratio, ipso attack, orientation in other ring systems. Quantitative treatment of reactivity in substrates and electrophiles. Diazonium coupling, Vilsmeir reaction, Gattermann-Koch reaction.

Aromatic Nucleophilic Substitution The SNAr SN1, benzyne and SRN1 mechanisms. Reactivity – effect of substrate structure, leaving group and attacking nucleophile. The von Richter, Sommelet-Hauser, and Smiles rearrangements. UNIT III

Free Radical Reactions Types of free radical reactions, free radical substitution mechanism, mechanism at an aromatic substrate, neighbouring group assistance. Reactivity for aliphatic and aromatic substrates at a bridgehead. Reactivity in the attacking radicals. The effect of solvents on reactivity.

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Allylic halogenation (NBS), oxidation of aldehydes to carboxylic acids, auto-oxidation, coupling of alkynes and arylation of aromatic compounds by diazonium salts, Sandmeyer reaction. Free radical rearrangement. Hunsdiecker reaction.

UNIT IV Addition to Carbon-Carbon Multiple Bouds Mechanistic and sterochemical aspects of addition reactions involving electrophiles, nucleophiles and free radicals, regio- and chemoselectivity, orientation and reactivity. Addition to cyclopropane ring. Hydrogenation of double and triple bonds, hydrogenation of aromatic rings. Hydroboration. Michael reaction. Sharpless asymmetric epoxidatio.

Addition to Carbon-Hetero Multiple Bonds Mechanism of metal hydride reduction of saturated and unsaturated carbonyl compounds, acids, esters and nitriles. Addition of Grignard reagents, organozinc and organolithium reagents to carbonyl and unsaturated carbonyl compounds. Wittig reaction. Meehanism of condensation reactions involving enolates – Aldol, Knoevenagel, Claisen, Mannich, Benzoin, Perkin and Stobbe reactions. Hydrolhysis of esters and amides, ammonolysis of esters.

UNIT V Elimination Reactions The E2, E1 and E1cB mechanisms and their spectrum, Orientation of the double bond. Reactivity – effects of substrate structures, attacking base, the leaving group and the medium. Mechanism and orientation in pyrolytic elimination.

Books Suggested: 1. Advanced Organic Chemistry-Reactions, Mechanism and Structure, Jerry March, John Wiley. 2. Advanced Organic Chemistry, F.A. Carey and R.J.Sundberg, Plenum. 3. A Guide Book to Mechanism in Organic Chemistry, Peter Sykes, Longman. 4. Structure and Mechanism in Organic Chemistry, C.K.Ingold, Cornell University Press. 5. Organic Chemistry, R.T. Morrison and R.N.Boyd, Prentice-Hall 6. Modern Organic Reactions, H.O. House, Benjamin. 7. Principles of Organic Synthesis, R.O.C. Norman and J.M.Coxon, Blackie Academic & Professional. 8. Pericyclic Reactions, S.M. Mukherji, Macmillan, India. 9. Stereochemistry of Organic Compounds, D. Nasipuri, New Age International. 13

CH 406 PHYSICAL CHEMISTRY UNIT I Quantum Chemistry Introduction to Exact Quantum Mechanical Results The Schrodinger equation and the postulates of quantum mechanics. Discussion of solutions of the Schrodinger equation to some model systems viz., particle in 1 and 3dimensional box, the harmonic oscillator, the hydrogen atom. Approximate Methods: The variation theorem, linear variation principle. UNIT II

Quantum Chemistry Electronic Structure of Atoms: Russell-Saunders terms and coupling schemes, spectral terms for pn configurations and dn configurations, Magnetic effects: Normal and anomalous Zeeman effects. Molecular Orbital Theory, Huckel theory of linear conjugated systems, bond order and charge density calculations. Applications to ethylene, butadiene. UNIT III

Thermodynamics Classical Thermodynamics Partial molar properties; partial molar free energy – chemical potential, partial molar volume and partial molar heat content. Gibbs – Duhem equation, variation of chemical potential with temperature and pressure, chemical potential for ideal gas. Thermodynamic derivation of law of mass action. Concept of fugacity and determination of fugacity. Themodynamic derivation of phase rule, application of phase rule to three component systems; second order phase transitions. UNIT IV

Statistical Thermodynamics Concepts of phase space, microstate and macrostate. Ensemble averaging, Canonical, grand canonical and microcanonical ensembles, Maxwell-Boltzman distribution laws (using Lagrange’s method of undetermined multipliers). Partition functions – translational, rotational, vibrational and electronic partition functions, calculation of thermodynamic properties in terms of partition functionsEnergy, specific heat at constant volume and constant pressure, entropy, work function, pressure Gibb’s free energy and chemical potential. Chemical equilibria and equilibrium constant in terms of partition functions, Fermi-Dirac statistics – distribution law and Bose-Einstein statistics – distribution law.

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UNIT V Non Equilibrium Thermodynamics Thermodynamic criteria for non-equilibrium states, entropy production and entropy flow, entropy balance equations for different irreversible processes (e.g. heat flow, chemical reaction etc.) transformations of the generalized fluxes and forces, non equilibrium stationary states, phenomenological equations, microscopic revensibility and Onsager’s reciprocity relations, electrokinetic phenomena, diffusion, electric conduction. Books Suggested: 1. 2. 3. 4. 5. 6. 7.

Physical Chemistry, P.W. Atkins, ELBS. Introduction to Quantium Chemistry, A.K. Chandra, Tata McGraw Hill. Quantum Chemistry, Ira N. Levine, Prentice Hall. Coulson’s Valence, R. McWeeny, ELBS. Theoretical Chemistry, S. Glasston, Princeton, London. Non Equilibrium Thermodynamics, Fitts, McGraw Hills, New York. Fundamentals of Chemical GThermodynamics, E.N.Yeremin, Mir Publishers.

CH 408 GROUP THEORY, SPECTROSCOPY AND DIFFRACTION

METHODS UNIT I Group Theory: Symmetry elements and symmetry operation, definitions of group, subgroup, Group and subgroup. Schonflies symbols, representations of groups by matrices (representation for the Cn, Cnv, Cnh, Dnh etc. groups to be worked out explicitly.). Character of a representation. The great orthogonality theorem (without proof) and its importance. Character tables and their use in spectroscopy

UNIT II Photoelectron Spectroscopy : Photo-electric effect, ionizagtion process, Koopman’s theorem. Photoelectron spectra of simple molecules. Electronically excited states: Fluorescence, phosphorescence and Chemiluminscence; Fluorescence Spectroscopy: Principle, basic instrumentation and Applications.

UNIT III Nuclear Magnetic Resonance Spectroscopy (NMR): Theory of NMR: Nuclear spin, nuclear resonance, saturation, shielding of magnetic nuclei, deshielding; Chemical Shift and its measurements, factors influencing chemical shift; Spin-spin interactions, factors influencing coupling constant ‘J’ Spin decoupling; Instrument –basic ideas; Applications of NMR; Basic idea of 13C NMR and FT NMR, advantages of FT NMR. 15

UNIT IV Electron Spin Resonance Spectroscopy(ESR): Basic principle: zero field splitting, factors affecting the ‘g’ value. Isotropic and anisotropic hyperfine coupling constants, spin Hamiltonian, spin densities, Measurement techniques, ESR instrumentation and applications.

UNIT V Diffraction Techniques : Miller indices; X-ray diffraction – Bragg Law, Laue method; Debye-Scherrer method of X-ray structural analysis of crystals; Index reflections; Identification of unit cells from systematic absences in diffration pattern; X-ray diffration method for Identification of crystalline compound. Books Suggested: 1. Modern Spectroscopy, J.M.Hollas, John Wiley. 2. Applied Electron Spectroscopy for Chemical Analysis Ed. H. Windawi and F.L.Ho, Wiley Interscience. 3. NMR, NQR, EPR and Mossbauer Spectroscopy in Inorganic Chemistry, R.V.Parish, Ellis Harwood. 4. Physical Methods in Chemistry, R.S.Drago, Saunders College. 5. Chemical Applications of Group Theory. F.A. Cotton 6. Indroduction to Molecular Spectroscopy, G.M.Barrow, McGraw Hill 7. Basic Principles of Spectroscopy. R. Chang, McGraw Hill 8. Theory and Applications of UV Spectroscopy, H.H.jaffe and M. Orchin, IBHOxford. 9. Introduction to Photoelectron Spectroscopy, P.K.Ghosh, John Wiley 10. Introduction to Magnetic Resonance, A. Carrington and A.D.Maclachalan, Harper & Row. 11. Principles of Instrumentation Analysis, D.A. Skoog and J.J.Leary Publ Saunders, USA

CH 411 LABORATORY COURSE II Organic Chemistry Qualitative Analysis Separation, purification and identification of compounds of binary mixture (one liquid and one solid), chemical tests, Interpretation of IR Spectra of simple compounds.

Organic Synthesis Acetylation: Acetylation of glucose and hydroquinone. Oxidation: Adipic acid by chromic acid oxidation of cyclohexanol. 16

Cannizzaro reaction: 4-Chlorobenzaldehyde as substrate. Aromatic electrophilic substitutions: Synthesis of p-nitroaniline and p-bromoaniline.

Quantitative Analysis Determination of the percentage or number of hydroxyl group in an organic compound by acetylation method. Estimation of amines/phenols using bromate bromide solution/or acetylation method. Determination of Iodine and Saponification values of an oil sample. Determination of DO, COD and BOD of water sample. CH 412 PHYSICAL CHEMISTRY

Adsorption (a) To study surface tension – concentration relationship for solutions (Gibbs equation) and hence determine the limiting cross-sectional area of molecule. (b) To study the adsorption of acetic acid/oxalic acid by activated charcoal and verification of Freundlich and Langmuir’s isotherms.

Phase Equilibria (i) (ii) (iii)

Determination of congruent composition and temperature of a binary system (e.g. diphenylamine-benzophenone system). Determination of glass transition temperature of a given salt (e.g. CaCl2) by solubility method. To construct the phase diagram for three component system (e.g. Chloroformaacetic acid-water)

Electrochemistry

Conductometry (i) (ii) (iii)

To determine the strength of weak acid using NaOH conductometrically. To determine the strength of strong and weak acids in a given mixture conductometrically. To find out basicity of given acid (mono- di-and tribasic) conductometrically.

Polarimetry/Refractometry (i) (ii)

To determine the specific rotation of a given optically active compound. To verify the law of refraction of mixture (e.g. glycerol and water) using Abbe’s refractometer.

Books Suggested: 1. Vogel’s Textbook of Quantitative Analysis, (revised) 17

2. Synthesis and Characterization of Inorganic Compounds, W.L. Jolly Prentice Hall. 3. Experiments and Techniques in Organic Chemistry, D. Pasto, C. Johnson and M. Miller, Prentice Hall. 4. Macroscale and Microscale Organic Experiments, K.L. Williamson, D.C. Heath. 5. Systematic Qualitative Organic Analysis, H. Middleton, Adward Arnold. 6. Handbook of Organic Analysis – Qualitative and Quantitative, H. Clark, Adward Arnold. 7. Vogel’s Textbook of Practical Organic Chemistry, A.R. Tatchell, John Wiley. 8. Practical Physical Chemistry, A.M. James and F.E. Prichard, Longman 9. Findley’s Practical Physical Chemistry, B.P.Levitt, Longman 10. Experimental Physical Chemistry, R.C. Das and B. Behera, Tata McGraw Hill 11. Advanced Practical Physical Chemistry, J.B. Yadav, Goel Publishing House. 12. Adevanced Experimental Chemistry, Vol. I – Physical J.N.Gurtu and R.Kapoor, S. Chand & Co.

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M Sc II YEAR-2013-14 SEMESTER III CH-501 APPLICATIONS OF SPECTROSCOPY Inorganic Chemistry UNIT I Vibrational Spectroscopy Symmetry and shapes of AB2, AB3, AB4, AB5 and AB6, mode of bonding of ambidentate ligands, ethylenediamine and diketonato complexes, application of resonance Raman spectroscopy particularly for the study of active sites of metalloproteins. Electron Spin Resonance Spectroscopy Hyperfine coupling, spin polarization for atoms and transition metal ions, spinorbit coupling and significance of g-tensors, application to transition metal complexes (having one unpaired electron) including biological systems and to inorganic free radicals such as PH4, F2 and [BH3]. UNIT II Nuclear Magnetic Resonance of Paramagnetic Substances in Solution The contact and pseudo contact shifts, factors affecting nuclear relaxation, some applications including biochemical systems, an overview of NMR of metal nuclides with emphasis on 195 Pt and 199Sn NMR. Mossbauer Spectroscopy Basic principles, spectral parameters and spectrum display. Application of the technique to the studies of (1) bonding and structures of Fe+2 and Fe+3 compounds including those of intermediate spin, (2) Sn+2 and Sn+4 compounds – nature of ML bond, coordination number, structure and (3) detection of oxidation state and inequivalent MB atoms. Organic Chemistry UNIT III Ultraviolet and Visible Spectroscopy Various electronic transitions (185-800 nm), Beer-Lambert law, effect of solvent on electronic transitions, ultraviolet bands for carbonyl compounds, unsaturated carbonyl compounds, dienes, conjugated polyenes. Fieser-Woodward rules for conjugated dienes and carbonyl compounds, ultraviolet spectra of aromatic and heterocyclic compounds. Steric effect in biphenyls. Mass Spectrometry Introduction, ion production – El, Cl, FD and FAB, factors affecting fragmentation, ion analysis, ion abundance. Mass spectral framentation of organic compounds, common functional groups, molecular ion peak, metastable peak, McLafferty rearrangement. Nitrogen rule. High resolution mass spectrometery. Examples of mass spectral fragmentation of organic compounds with respect to their structure determination.

UNIT IV 19

Infrared Spectroscopy Instrumentation and sample handling. Characteristic vibrational frequencies of alkanes, alkenes, alkynes, aromatic compounds, alcohols, ethers, phenols and amines. Detailed study of vibrational frequencies of carbonyl compounds (ketones, aldehydes, esters, amides, acids, anhydrides, lactones, lalctams and conjugated carbonyl compounds). Effect of hydrogen bonding and solvent effect on vibrational frequencies, overtones, combination bands and Fermi resonance. FT IR. IR of gaseous, solids and polymeric materials. Optical Rotatory Dispersion (ORD) and Circular Dichroism (CD) Definition, deduction of absolute configuration, octant rule for ketones.

UNIT V Nuclear Magnetic Resonance Spectroscopy General introduction and definition, chemical shift, spin-spin interaction, shielding mechanism, mechanism of measurement, chemical shift values and correlation for protons bonded to carbon (aliphatic, olefinic, aldehydic and aromatic) and other nuclei (alcohols, phenols, enols, carboxylic acids, amines, amides & mercapto), chemical exchange, effect of deuteration, complex spin-spin interaction between two, three, four and five nuclei (first order spectra), virtual coupling. Stereochemistry, hindered rotation, Karplus curve-variation of coupling constant with dihedral angle. Simplification of complex spectra-nuclear magnetic double resonance, contact shift reagents, solvent effects. Fourier transform technique, nuclear Overhauser effect (NOE). Resonance of other nuclei-F, P. Carbon-13 NMR Spectroscopy General considerations, chemical shift (aliphatic, olefinic, alkyne, aromatic, heteroaromatic and carbonyl carbon), coupling constants. Two dimension NMR spectroscopy – COSY, NOESY, DEPT, INEPT, APT and INADEQUATE techniques. Books Suggested: 1. Structural Methods in Inorganic Chemistry, E.A.V. Ebsworth, D.W.H. Rankin and S. Cradock, ELBS. 2. Infrared and Raman Spectra: Inorganic and Coordination Compounds, K. Nakamoto, Wiley. 3. Progress in Inorganic Chemistry vol., 8 ed., F.A. Cotton, vol., 15, ed. S.J. Lippard, Wiley. 4. Inorganic Electronic Spectroscopy., A.P.B. Lever, Elsevier. 5. NMR, NQR, EPR and Mossbauer Spectroscopy in Inorganic Chemistry, R.V. Parish, Ellis Horwood. 6. Practical NMR Spectroscopy, M.L. Martin, J.J. Delpeuch and G.J. Martin, Heyden. 7. Spectrometric Identification of Organic Compounds, R.M. Silverstein, G.C. Bassler and T.C. Morrill, John Wiley. 8. Introduction to NMR Spectyroscopy, R.J. Abraham, J. Fisher and P. Loftus, Wiley. 20

9. Application of Spectroscopy of Organic Compounds, J.R. dyer, Prentice Hall. 10. Spectroscopic Methods in Organic Chemistry, D.H. Williams, I. Fleming, Tata McGraw-Hill.

CH-502 Photochemistry and Solid State Chemistry UNIT I Photochemical Reactions Interaction of electromagnetic radiation with matter, types of excitations, fate of excited molecule, quantum yield, transfer of excitation energy, actinometry. Determination of Reaction Mechanism Classification, rate constants and life times of reactive energy states – determination of rate constants of reactions. Effect of light intensity on the rate of photochemical reactions. Types of photochemical reactions – photo-dissociation, gas-phase photolysis. UNIT II Photochemistry of Alkenes Intramolecular reactions of the olefinic bond – geometrical isomerism, cyclisation reactions, rearrangement of 1,4- and 1,5- dienes, Photochemistry of Carbonyl Compounds Intramolecular reactions of carbonyl compounds – saturated, cyclic and acyclic, β,γ - unsaturated and α,β-unsaturated compounds. Cyclohexadienones. Intermolecular cyloaddition reactions – dimerisations and oxetane formation. UNIT III Photochemistry of Aromatic Compounds Isomerisations, additions and substitutions. Miscellaneous Photochemical Reactions Photo-Fries reactions of anilides. Photo-Fries rearrangement. Barton reaction. Singlet molecular oxygen reactions. Photochemical formation of smog. Photodegradation of polymers. Photochemistry of vision.

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UNIT IV Solid State Reactions General principles, experimental procedures, Crystal Defects – Perfect and imperfect crystals, intrinsic and extrinsic defects – point defects, line and plane defects. Thermodynamics of Schottky and Frenkel defect formation, colour centers. UNIT V: Solid State Chemistry Electronic Properties and Band Theory Metals, insulators and semiconductors, band theory of solids(qualitative treatments), band structure of metals, insulators and semiconductors. Inrinsic and extrinsic semiconductors, p-n junctions. Superconductors- factors affecting the super conductivity, magnetic properties, persistent current and BCS theory of superconductors. Optical properties – photoconduction. Magnetic Properties – Classification of materials, Magnetic domains, hysteresius. Organic Solids Electrically conducting solids, organic charge transfer complex - new superconductors. Books Suggested: 1.Fundamentals of Photochemistry, K.K Rohtagi-Mukherji, Wiley- Easter. 2. Molecular Photochemistry, N.J. Turro, W.A. Benjamin. 3. Introductory Photochemistry, A. Cox and T. Camp, McGraw-Hill. 4. Photochemistry, R.P. Kundall and A. Gilbert, Thomson Nelson. 5.Organic Photochemistry, J. Coxon and B. Halton, Cambridge University Press. 6.Solid State Chemistry and its Applications, A.R. West, Plenum. 7. Principles of the Solid State, H.V. Keer, Wiley Eastern. 8.Solid State Chemistry, N.B. Hannay. 9. Solid State Chemistry, D.K. Chakrabarty, New Age International.

CH-503 ENVIRONMENTAL CHEMISTRY

UNIT I Environment Introduction. Composition of atmosphere, vertical temperature, heat budget of the earth atmospheric system, vertical stability atmosphere. Biogeochemical cycles of C, N, P, S and O. Biodistribution of elements. 22

UNIT II Hydrosphere Chemical composition of water bodies:lakes, streams, rivers and wet lands, etc. Hydrological cycle. Aquatic pollution – inorganic, organic, pesticide, agricultural, industrial and sewage, detergents, oil spills and oil pollutants. Water quality parameters – dissolved oxygen (DO), biochemical oxygen demand(BOD), solids, metals, content of chloride, sulphate, phosphate, nitrate and micro-organisms. Water quality standard. Analytical methods for measuring BOD, DO, COD, F. Oils, metals (As , Cd, Cr, Hg, Pb. Se etc.), residual chloride and chlorine demand. Purification and treatment of water.

UNIT III Lithosphere : All types of soils Composition, micro nutrients, Pollution: fertilizers, pesticides, plastics and metals. Waste treatment.

UNIT IV Atmosphere Chemical composition of atmosphere – particles, ions and radicals and their formation. Chemical and photochemical reactions in atmosphere, smog formation, oxides of N, C, S, O and their effect, pollution by chemicals, petroleum, minerals, chlorofluorohydrocarbons. Green house effect, acid rain, air pollution controls and their chemistry. Analytical methods for measuring air pollutants. Continuous monitoring instruments.

UNIT V Industrial Pollution and Environmental Toxicology Cement, sugar, distillery, drug, paper and pulp, thermal power plants, nuclear power plants, metallurgy. Polymers, drugs etc. Radionuclide analysis. Disposal of wastes and their management. 23

Chemical solutions to environmental problems, biodegradability, principles of decomposition, better industrial processes. Bhopal gas tragedy. Chemobyl, Three mile island, Sewozo and Minamata disaster. Books Suggested: 1. 2. 3 4. 5.

Environmental Chemistry, S.E. Manahan, Lewis Publishers. Environmental Chemistry, Sharma & Kaur, Krishna Publishers. Environmental Chemistry, A.K. De, Wiley Eastern. Environmental Pollution analysis, S.M. Khopkar, Wiley Eastern. Standard Method of Chemical Analysis, F.J. Welcher Vol, Van Nostrand Reinhold Co. 6. Environmental Analysis of Airborne Particles, Ed. S. Landsberger and M. Creatchman, Gordon and Breach Science Publication. 7. Environmental Chemistry, S. Baird, W.H. freeman.

CH-504 BIO-CHEMISTRY UNIT I Metal ions in Biological Systems Role of metal ions in biological processes. Bioenergetics and ATP Cycle: Photosynthesis, Chlorophylls, Photosystem I and Photosystem II. Diosygen Uptake: Structure and function of haemoglobin, myoglobin, hemocyanins and hemerythrin, model system and synthetic complexes of iron Cobalt and copper. Electron Transfer in Biology: Structure and function of metalloproteins, Cytochromes and iron-sulphur proteins, synthetic models, peroxidases and cataluses. Nitrogenases: Biological nitrogen fixation, molyhydenum nitrogenases, model systems.

UNIT II Enzymes Introduction and historical perspective, chemical and biological catalysis, remarkable properties of enzymes like catalytic power, specificity and regulation. Nomenclature and classification. Fischer’s lock and key and Koshland’s induced fit hypothesis, concept and identification of active site by the use of inhibitors, affinity labelling and enzyme modification by site directed muta genesis. Transition state theory, orientation and stearic effect, acid-base catalysis, covalent catalysis, strain or distortion. Coupling of ATP cleavage to endergonic processes, β-cleavage and condensation.

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UNIT III Co-Enzyme Chemistry Cofactors as derived from vitamins, coenzyme, prosthetic groups, apoenzymes. Structure and biological functions of coenzyme A, thiamine pyrophosphate, pyridoxal phosphate, NAD+, NADP+, FMN, FAD, lipoic acid, vitamin B12, Mechanism of reaction catalysed by the above cofactors. Large-scale production and purification of enzymes, techniques and methods of immobilization of enzymes, effect of immobilization on enzyme activity, application of immobilized enzymes, use of enzymes infood and drink industry, brewing and cheesemaking, syrups from corn starch. UNIT IV Bioenergetic and Biopolymer Interactions: Standard free energy change in biochemical reactions, exergonic, endergonic. Hydrolysis of ATP, synthesis of ATP from ADP. Forces involved in biopolymer interactions. Electrostatic charges and molecular expansion, hydrophobic forces, dispersion force interactions. Multiple equilibria and various types of binding processes in biological systems. Hydrogen ion titration curves.

UNIT V Diffraction Methods and Statistical Mechanics in Biopolymers. Evaluation of size, shape, molecular weight and textent of hydration of biopolymers by various experimental techniques. Light scattering, low angle Xray scattering, X-ray diffraction and photo correlation spectroscopy ORD Chain configuration of macromolecules, statistical distribution end to end dimensions, calculation of average dimensions for various chain structure. Polypeptide and protein structures, introduction to protein folding problem.

Books Suggested : 1. The Inorganic Chemistry of Biological Processes, M.N.Hughes Wiles (1972). 2. Bioinorganic Chemistry-An Introduction, Enchiroochiai. 3. Principles of Bioinorganic Chemistry, S.J. Lippard and J.M.Berg, University Science Books. 4. Bioinorganic Chemistry, I Bertini, H.B. Gray, S.J.Lipard and J.S. Valentine, University Science Books. 5. Bioorganic Chemistry: A Chemical Approach to Enzyme Action, Hermann Dugas and C.Penny, Springer-Verlag. 6. Understanding Enzymes, Trevor Palmer, Prentice Hall. 25

7. Enzyme Chemistry:Impact and Applications, Ed. Collin J. Suckling, Chapman and Hall. 8. Enzyme Mechanisms Ed. M.I.Page and A.Williams, Royal Society of Chemistry. 9. Fundamentals of Enzymology, N.C. Price and L. Stevens, Oxford University Press. 10. Immobilized Enzymes: An Introduction and Applications in Biotechnology, Michael D. Tevan, John Wiley. 11. Enzymatic Reaction Mechanisms, C.Walsh, W.H. freeman. 12. Enzynie Structure and Mechanism, A Fersht, W.H. Freeman. 13. Biochemistry: The Chemical Reactions of Living Cells, D.E.Metzler, Academic Press. 14. Principles of Biochemistry, A.L.Lehninger, Worth Publishers. 15. Biochemistry, L. Strver, W.H.Freeman 16. Biochemistry, J.David Rawn, Neil Patterson. 17. Biochemistry, Voet and Voet, John Wiley. 18. Outlines of Biochemistry, E.E.Conn and P.K.Stumpf, Johh Wiley. 19. Bioorganic Chemistry: A Chemical Approach to Enzyme Achon. H. Dugas and C.Penny, Springer-Verlag. 20. Macromolecules: Structure and Function, F.World, Prentice Hall.

Course No.511 : Inorganic Chemistry – Laboratory Course 1. Experiment No. 1 : Preparation of some Inorganic coordination compounds. Experiment No. 2: Analysis the given mixture for four rare elements. Experiment No. 3: Estimation of three constituent in the given mixture (Two gravimetrically and one volumetrically). Experiment No. 4: variations.

Iron phenanthroline complex : Job’s Method of continuous

Experiment No. 5: Method.

Find out the stability constant of metal complex by Bjerrum’s

CH 512 : Instrumental Lab. – Lab. Course II. I . pH metry: 1. To determine the dissociation constants of dibasic and tribasic acids. 26

2. Titration of mixture of acids (Hcl + CH3 CooH) again strong base. II. Spectrophotometry: 1. Determination of Pka of an indicator (e.g. methyl red) in (a) aqueous and (b) micellor meda. 2. Defermination of stoichiometry and stability constant of inorganic (e.g. ferri – salcy7clic acid) and organic (e.g. amine – iodine). 3. To determine the concentration of chromium and manganese in a binary mixture. III. Polarography: 1. To study oxygen wave by polorography. 2. To characterize and determine Pb2+. Cd2+ and Zn2+ , ions by polarography/ cyclic voltammetry

IV Fluorometry 1. Determination of strength of Vitamin B (Riboflavin) and Aluminium. V. Nephelometry 1. Determination of sulphate content in water sample. 2. Determination of phosphate content in water sample. VI. Flame photometry 1. Estimation of Ma, K and Ca. 2. Estimation in a mixture (Na and K; K and Ca). VII Water and Waste Water examination: 1. DO and BOD determination. 2. COD estimation. 3.Fluoride and nitrate determination. VIII Cement Analysis IX Chromatography: Coloumn

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M Sc II YEAR (Affiliated college)-2013-14 SEMESTER IV A student has to take any one of the following four groups of elective papers. LIST OF ELECTIVE PAPERS IN THE M.Sc. CHEMISTRY. GROUP A CH 601 :Organotransition Metal Chemistry. CH 602 : Advanced Analytical Techniques CH 603 : Liquid State CH 604 : Polymers GROUP B CH 611 : Photoinorganic Chemistry CH 612 : Organic Syntehsis-I CH 613 :Organic Synthesis-II CH 614 : Surfactants GROUP C CH 621 : Bioinorganic and Supramolecular Chemistry CH 622 : Heterocyclic Chemistry CH 623 : Chemistry of Natural Products CH 624 : Electrochemistry GROUP D CH 631 : Nuclear and Radiochemistry CH 632 : Medicinal Chemistry CH 633 : Physical Organic Chemistry CH 634 : Chemistry of Materials

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ELECTIVE PAPER 1 CH-601

Organotransition Metal Chemistry

UNIT I Organotransition metal compounds : Difinihon, Classification and nomenclature of organotransition metal compounds. Difference in nature of bonding between metal carbonyls and organotransition metal compounds. UNIT II Alkyls and Aryls of Transition Metals: Types, methods of synthesis, thermal stability and decomposition pathways. UNIT III

Transition Metal π-Complexes Transition metal π-complexes with unsaturated organic molecules, alkenes, cyclopentadienyls and arenas, methods of synthesis, properties, nature of bonding and structural features. UNIT IV

Homogeneous Catalysis

Homogeneous catalytic hydrogenation of Alkenes, Zeigler Natta polymerization of olefins, Isomerisation of Alkenes, Hydroformylation, Dimerisation and polymerization of Alkenes and Alkynes. UNIT V Organocopper in Organic Synthesis : Conjugated additions, halogen substitution, alkylation of epoxides, alkylation of allylacetates, ketones from acid chlorides.

Books Suggested: 29

1. Principles and Application of Organotransition Metal Chemistry, J.P. Collman, L.S. Hegsdus, J.R. Norton and R.G. Finke, University Science Books. 2. The Organomettalic Chemistry of the Transition Metals, R.H. Crabtree, John, Wiley. 3. Metallo-organic Chemistry, A.J. pearson, Wiley. 4. Organometallic Chemistry, R.C. Mehrotra and A. Singh, New Age International.

ELECTIVE PAPER 2 CH-602 Advanced Analytical Techniques Unit I Basics of Instrumentation and Gas Chromatography Basic Electronics for Analytical Instruments; Automation in Analysis: Introduction to On-line/ Process control analyzer, Discrete, Continuous analysis and Flow injection analysis Gas Chromatography (GC): Theory, General layout of equipment, detectors for GC, Applications; Gas Chromatography with Mass Spectrometry (GC-MS). Unit II Column and Thin Layer Chromatography High performance Liquid Chromatography (HPLC): Types of Liquid Chromatography, General layout of equipment & detectors for HPLC, Applications of HPLC in pharmaceutical Analysis. Thin Layer Chromatography (TLC), Application of TLC special reference to forensic analysis; High Performance Thin Layer Chromatography (HPTLC). Unit III X-ray and Emission Techniques: Production of X-rays, Instrumentation, direct X-ray method, X-ray Absorption Spectroscopy, X-ray Fluorescence Spectroscopy. Inductively Coupled Plasma Emission Spectroscopy (ICPES): theory, instrumentation and applications. Unit IV Surface Techniques: Basic Principle, Theory; Chemical & Surface applications of: Electron Spectroscopy for Chemical Analysis (ESCA), Auger Emission Spectroscopy (AES), Photoacoustic Spectroscopy (PAS) Unit V Tools for Nanotechnology: Basic Principle, Instrumentation and Significance of Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM). Books: 1. Instrumental Methods of Analysis, H.H. Willard, L.L. Merritt, J.A. Dean and F.A. Settle, CBS Publ. Delhi. 5. Principles of Instrumental Analysis, D.A. Skoog and J.L. Loary, Publ. W B Saunders 6. Instrumental Methods of Analysis, Strobel 30

7. Instrumental Methods of Analysis, H.H. Willard, L.L. Merritt, J.A. Dean and F.A. Settle , CBS Publ. Delhi. 8. Nanoscale materials, L.M. L. Marzan, Prashant V.Kamat, Publ. Springer 2003 9. Nanoscale Science and Technology, R.w. Kelsall, M. Geoghegan I.w. Hamley Publ John Wiely & Sons 2005


Liquid State

UNIT I General Properties of Liquids Properties of liquids, Structure of liquids, Comparison of liquid Argon and liquid sodium. Some thermodynamic relations, equations of state, critical constants. Different types of intermolecular forces in liquids, Order on liquids. UNIT II Theories of Liquids A classical partition function for liquids, correspondence principle, configuration properties: configuration integral. Theory of liquids: cell theory, model approach; single cell models, communal energy and entropy. UNIT III

Distribution Function and Related Equations Molecular distribution functions, pair distribution function. Internal energy of liquids. Relationship between pair distribution function and pair potential function. The YBG equation, the HNC equation, the PY equation, cluster expansion. UNIT IV

Methods for Structure Determination and Computational Techniques Spectroscopic techniques for liquid dynamic structure studies, Neutron and X-ray scattering spectroscopy. Computation Techniques-Monte Carlo and molecular dynamics methods. UNIT V 31

Super cooled and Ionic Liquids Super cooled and ionic liquids, theories of transport properties; non Arrhenius behaviour of transport properties, Quantum liquids: Comparison of classical and quantum liquids. Critical velocity for superfluids.

Books Suggested: 1. 2. 3. 4. 5. 6.

An Introduction to Liquid State, P.A. Egelstaff, Academic Press. The Dynamic Liquid State, A.F.M. Barton, Longman. Introduction to Statistical Thermodynamics, T.L. Hill, Addison Wiley. The Liquid State, J.A. Pryde. Significant Liquid Structures, H. Eyring and M.S. John. Properties of liquids and solutions, Murrel & Boucher, John Wiley & Sons

ELECTIVE PAPER 4 CH-604 Polymers UNIT I Basic Importance of polymers. Basic concepts : Monomers, repeat units, degree of polymerization. Linear, branched and network polymers. Classification of polymers. Polymerization: condensation, addition, radical chain-ionic and co-ordination and co-polymerization. Polymerization conditions and polymer reactions. Polymerization in homogeneous and heterogeneous systems. UNIT II Polymer Characterization Polydispersion-average molecular weight concept. Number, weight and viscocity average molecular weights. Polydispersity and molecular weight distribution. The practical significance of molecular weight. Measurement of molecular weights. End-group, viscocity, light scattering, osmotic and ultracentrifugation methods. Analysis and testing of polymers-chemical analysis of polymers, spectroscopic methods, X-ray diffraction study. Microscopy. Thermal analysis and physical testing-tensile strength, impace. Tear resistance. Hardness and abrasion resistance.

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UNIT III Structure and Properties Morophology and order in crystalline polymers-configurations of polymer chains. Crystal structures of polymers. Morphology of crystalline polymers, straininduced morphology, crystallization and melting. Polymer structure and physical properties-crystalline melting point Tm-melting points of homogeneous series, effect of chain flexibility and other steric factors, entropy and heat of fusion. The glass transition temperature, Tg-Relationship between Tm and Tg, effects of molecular weight, diluents, chemical structure, chain topology, branching and cross linking. Property requirements and polymer utilization. UNIT IV Polymer Processing Plastics, elastomers and fibres. Compounding. Processing techniques: Calendering, die casting, rotational casting, film casting, injection moulding, blow moulding, extrusion moulding, thermoforming, foaming, reinforcing and fibre spining. UNIT V Properties of Commercial Polymers Polyethylene, polyvinyl chloride, polyamides, polyesters, phenolic resins, epoxy resins and silicone polymers. Functional polymers – Fire retarding polymers and electrically conducting polymers. Biomedical polymers – contact lens, dental polymers, artificial heart, kidney, skin and blood cells. Books Suggested: 1. Textbook of Polymer Science, F.W. Billmeyer Jr. Wiley. 2. Polymer Science, V.R. Gowariker, N.V. Viswanathan and J. Screedhar, Wiley-Eastern. 3. Functional Monomers and Polymers, K. Takemoto, Y. Inaki and RM. Ottanbrite. 4. Contemporary Polymer Chemistry, H.R. Alcock and F.W. Lambe, Prentice Hall. 5. Physics and Chemistry of Polymers, J.M.G. Gowie, Blackie Academic and Professional.

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ELECTIVE PAPER 5

CH-611

Photoinorganic Chemistry

UNIT I

Basics of Photochemistry Absorption, excitation, photochemical laws, quantum yield, electronically excited states-life times-measurements of the times. Flash photolysis, stopped flow techniques. Energy dissipation by radiative and non-radiative processes, absorption spectra, Franck-Condon principle, photochemical stages – primary and secondary processes. UNIT II

Properties of Excited States Structure, dipole moment, acid-base strengths, reactivity. Photochemical kineticscalculation of rates of radiative processes. Bimolecular deactivation – quenching.

Excited States of Metal Complexes Excited states of metal complexes: comparison with organic compounds, electronically excited states of metal complexes, charge-transfer spectra, charge transfer excitations, methods for obtaining charge-transfer spectra.

UNIT III

Ligand Field Photochemistry Photosubstitution, photooxidation and photoreduction, lability and selectivity, zero vibrational levels of ground state and excited state, energy content of excited

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state, zero-zero spectroscopic energy, development of the equations for redox potentials of the excited states.

UNIT IV

Redox Reactions by Excited Metal Complexes Energy transfer under conditions of weak interaction and strong interactionexciplex formation; conditions of the excited states to be useful as redox reactants, excited electron transfer, metal complexes as attractive candidates (2,2’ –bipyridyl and 1,10-phenanthroline complexes), illustration of reducing and oxidizing character of Ruthenium2+ (bipyridal complex, comparision with Fe(bipy)3; role of spin-orbit coupling-life time of these complexes. Application of redox processes of electronically excited states for catalytic purposes, transformation of low energy reactants into high energy products, chemical energy into light. UNIT V

Metal Complex Sensitizers Metal complex sensitizer, electron relay, metal colloid systems, semiconductor supported metal or oxide systems, water photolysis, nitrogen fixation and carbon dioxide reduction. Books Suggested: 1. Concepts of Inorganic Photochemistry, A.W. Adamson and P.D. Fleischauer, Wiley. 2. Inorganic Photochemistry, J. Chem., Educ., vol. 60, no. 10, 1983. 3. Progress in Inorganic Chemistry, vol. 30, ed. S.J. Lippard, Wiley. 4. Coordination Chem. Revs., 1981, vol. 39, 121, 131; 1975, 15, 321; 1990, 97, 313. 5. Photochemistry of Coordination Compounds, V. Balzai and V. Carassiti, Academic Press. 6. Elements of Inorganic Photochemistry, G.J. Ferraudi, Wiley.

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Organic Synthesis I

UNIT I Organometallic Reagents Principle, preparations, properties and applications of the following in organic synthesis with mechanistic details.

Group I and II metal organic compounds Li, Mg, Hg, Cd, Zn and Ce compounds.

Transition metals Cu, Pd, Ni, Fe, Co, Rh, Cr and Ti compounds.

Other elements S, Si, B and I compounds.

UNIT II

Oxidation Introduction, Different oxidative processes. Hydrocarbons- alkenes, aromatic rings, saturated C-H groups (activated and unactivated). Alcohols, diols, aldehydes, ketones, ketals and carboxylic acids. Amines, hydrazines, and sulphides. Oxidations with ruthenium tetraoxide, iodobenzene diacetate and thallium (III) nitrate.

UNIT III

Reduction 36

Introduction. Different reductive processes. Hydrocarbons – alkanes, alkenes, alkynes and aromatic rings. Carbonyl compounds – aldehydes, ketones, acids and their derivatives Epoxides. Nitro, nitroso, azo and oxime groups. Hydrogenolysis.

UNIT IV

Rearrangements General mechanistic considerations – nature of migration, migratory aptitude, memory effects. A detailed study of the following rearrangements: Pinacol-pinacolone, Wagner-Meerwein, Demjanov, Benzil-Benzilic acid, Favorskii, Arndt-Eistert synthesis, Neber, Beckmann, Hofmann, Curtius, Schmidt, Baeyer-Villiger, Shapiro reaction.

UNIT V

Metallocenes, Nonbenzenoid Aromatics and Polycyclic Aromatic Compounds. General considerations, synthesis and reactions of some representative compounds. Books Suggested: 1. Modern Synthetic Reactions, H.O. House, W.A. Benjamin. 2. Somer Modern Methods of Organic Synthesis, W. Carruthers, Cambridge Univ. Press. 3. Advanced Organic Chemistry, Reactions Mechanisms and Structure, J. March, John Wiley. 4. Principles of Organic Synthesis, R.O.C. Norman and J.M. Coxon, Blackie Academic & Professional. 5. Advanced Organic Chemistry Part B. F.A. Carey and R.J. Sundberg, Plenum Press. 6. Rodd’s Chemistry of Carbon Compounds, Ed. S. Coffey, Elsevier.

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Organic Synthesis II

UNIT I Disconnection Approach An introduction to synthons and synthetic equivalents, disconnection approach, functional group inter-conversions, the importance of the order of events in organic synthesis, one group C-X and two group C-X disconnections, chemoselectivity, reversal of polarity, cyclisation reactions, amine synthesis.

UNIT II

Protecting Groups Principle of protection of alcohol, amine, carbonyl and carboxyl groups.

Ring Synthesis Saturated heterocycles, synthesis of 3-, 4-, 5- and 6-membered rings, aromatic heterocycles in organic synthesis.

UNIT III

One Group C-C Disconnections Alcohols and carbonyl compounds, regioselectivity. Alkene synthesis, use of acetylenes and aliphatic nitro compounds in organic synthesis.

UNIT IV

Two Group C-C Disconnections Diels-Alder reaction, 1,3-difunctionalised compounds, α,β-unsaturated carbonyl compounds, control in carbonyl condensations, 1,5-difunctionalised compounds. Micheal addition and Robinson annelation.

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UNIT V

Synthesis of Some Complex Molecules Application of the above in the synthesis of following compounds: Camphor, Longifoline, Cortisone, Reserpine, vitamin D, Juvabione, Aphidicolin and Fredericamycin A. Books Suggested: 1. Designing Organic Synthesis, S. Warren, Wiley. 2. Organic Synthesis- Concept, Methods and Starting Materials, J. Fuhrhop and G. Penzillin, Verlage VCH. 3. Some Modern Methods of Organic Synthesis. W. Carruthers, Cambridge Univ. Press. 4. Modern Synthetic Reactions, H.O. House, W.A. Benjamin. 5. Advanced Organic Chemistry: Reactions, Mechanisms and Structure, J. March, Wiley. 6. Principles of Organic Synthesis, R. Norman and J.M. Coxon, Blackie Academic & Professional. 7. Advanced Organic Chemistry Part B, F. A. Carey and R.J. Sundberg, Plenum Press.


Surfactants:

UNIT I Characteristic Features of Surfactants. General structural features and behaviour of Surfactants. UNIT II

Micelle Formation by Surfactants Critical micelle concentration (cmc), micellar structure and shape, micellar, aggregation number, factors, affecting the value of cmc in aqueous medium. UNIT III 39

Solubilization by Solutions of Surfactants Solubilization in aqueous media; locus of solubilization, factors determing the extent of solubilization, effects of solubilization.

UNIT IV

Emulsification by Surfactants Formation of emulsions, factors determining emulsion stability, inversion of emulsions. UNIT V

Modification of Detergency by Surfactants Mechanisms of the cleaning process, effect of water hardness, builders, correlation between the chemical structure of the surfactant and its detergency. Books Suggested: 1. Surfactants and Interfacial Phenomenon. Milton J. Rosen, Johan-Wiley, 1978. 2. Solubilization by Surface Active Agents and Its Applications in Chemistry and Biologcal Sciences. P.H. Elworthy, A.T. Florence and C.B. McFarlane, Chapman and Hall, 1968. 3. Solution Behaviour of Surfactants, Theoretical and Applied Aspects, Volumes 1and 2 Edited by K.L. Mittal and E.J. Fendler, Plenum Press. 4. Technology of Textile Processing, Volume-V Chemistry of Textile Auxilliaries. V.A. Shenai, Sevak Publications, 1976.


Bioinorganic and Supramolecular Chemistry

UNIT I Metal storage Transport and Bio-mineralization: oxygen carrier (Hb & Mb), ferritin, transferrin and siderophores. Calcium in Biology: calcium in living cells, transport and regulation, moleculer aspects of intramoleculer process, extracellular binding protein, 40

Ca+2 ATP ase ,Ca+2 ATP ase structure, Ca+2 ATP ase reaction cycle, intracellular Ca+2 transport. UNIT II Metalloenzyms: Zinc enzymes- carboxy peptidase and carbonic anhydrase. Iron enzymes- Reactivity and structure of catalase, peroxidase and cytochrome P450, copper enzymes- Reactivity and structure of superoxide dimutase(SOD). Co enzyme vitamin B12 – Type, absorption, transport, metabolic function and structure.

UNIT III Metal nucleic acid interaction: metal ions and metal complex interaction, Metal complexes- nucleic acid. Metal in medicine: metal deficiency and disease, toxic effect of metals, metal used for diagnosis and chemotherapy with particular reference to anticancer drugs. UNIT IV Supramoleculer chemistry: Concepts and language moleculer recognization: molecular receptors for different types of molecules including arisonic substrates, design and synthesis of coreceptor molecules and multiple recognition. UNIT V Supramolecular reactivity and catalysis, supramolecular assemblies, supramolecular devices, supramolecular photochemistry, molecular and supra molecular photonic devices, supramolecular electronic, ionic and switching devices. Books suggested Principles of Bioinorganic chemistry, SJ Lippard and J.M. Berg, University science books. Bioinorganic chemistry, I Bertini, H.B. Garg, S.J. Lippard and J.S. Valentine, University science books. Inorganic Biochemistry, Vol I and II Ed. G.S. Eichhorn, Elsevier progress in inorganic chemistry Vol. 18 and 38 ed. J.J. Lippard, Wiley. Supra molecular chemistry, J.M. Lehn, VCH. Bioinorganic chemistry, A K. Das Books and allied (P) Ltd. Bioinorganic and supra molecular chemistry, Ajay kumar bhagi, G.R. Chatwal Himalaya publishing house.

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Heterocyclic Chemistry

UNIT I Nomenclature of heterocycles Systemic nomenclature of monocyclic, fused & bridge heterocycles. Three Membered Heterocyclic Compounds With One Hetero Atom: Aziridines, Oxiranes and Thiiranes Three Membered Heterocyclic Compounds With Two Hetero Atoms: Diaziridines, Diazirines and Oxaziridines UNIT II Four Membered Heterocyclic Compounds With One Hetero Atom: Azitines & Azitidines, Oxitanes, Thietanes and Carbonyl Derivatives: 2-Azitidinones and Oxetanone Bicyclic Ring Systems Derived from Pyrrole, Furan and Thiophene: Benzopyrroles, benzofurans and benzothiophenes UNIT III Five Membered Heterocyclic Compounds With One Hetero Atom: Tautomerism Pyrroles, Furans and Thiophenes Five Membered Heterocyclic Compounds With Two Hetero Atoms: Pyrazoles, Imidazoles, Oxazoles and Thiazoles

UNIT IV Six Membered Heterocyclic Compounds With One Hetero Atom: Pyridines, Pyrylium salts and α− and γ− Pyrones Six Membered Heterocyclic Compounds With Two Hetero Atoms: 42

Pyrazines, Pyridazines and Pyrimidines, Cinnolines and Phthalazines Quinazolines and Quinoxalines UNIT V Seven Membered Heterocyclic Compounds With Two Hetero Atoms: Azepines, Oxepins and Thiepins Bicyclic Ring Systems Derived from Pyridine: Quinoline and Isoquinolune Acridines and Phenanthridines Books Suggested: 1. Heterocyclic Chemistry Vol. 1-3, R.R. Gupta, M. Kumar and V. Gupta, Springer Verlag. 2. The Chemistry of Hetrocycles, T. Eicher and S. Hauptmann, Thieme. 3. Heterocyclic Chemistry, J.A. Joule, K. Mills and G.F. Smith, Chapman and Hall. 4. Heterocyclic Chemistry, T.L., Gilchrist, Longman Scientific Techinal. 5. Contemporary Heterocyclic Chemistry, G.R. Newkome and W.W. Paudler, Wiley-Inter Science. 6. An Introduction to the Heterocyclic Compounds, R.M. Acheson, John Wiley. 7. Comprehensive Heterocyclic Chemistry, A.R. Katritzky and C.W. Rees, eds. Pergamon Press.

ELECTIVE PAPER 11

CH-623

Chemistry of Natural Products

UNIT I

Terpenoids and Carotenoids Classification, nomenclature, occurrence, isolation, general methods of structure determination, isoprene rule, biosynthesis. Structure determination, stereochemistry, synthesis of the following representative molecules: Citral, Geraniol, α-Terpeneol, Farnesol, Zingiberene, Phytol, Abietic acid and β-Carotene.

43

UNIT II Alkaloids Definition, nomenclature and physiological action, occurrence, isolation, general methods of structure elucidation, degradation, classification based on nitrogen heterocyclic ring, role of alkaloids in plants, biosynthesis. Structure, stereochemistry, synthesis of the following: Ephedrine, (+)-Coniine, Nicotine, Quinine and Morphine.

UNIT III Steroids Occurrence, nomenclature, basic skeleton, Diel’s hydrocarbon, stereochemistry, biosynthesis. Isolation, structure determination of Cholesterol and Bile acids.

UNIT IV

Plant Pigments Occurrence, nomenclature and general methods of structure determination. Isolation structure and synthesis of Apigenin, Luteolin,Quercetin, Myrcetin, Vitexin, Diadzein, Butein, Aureusin, Cyanidin, Hirsutidin. Biosynthesis of flavonoids : Acetate pathway and Shikimic acid pathway.

UNIT V

Porphyrins Structure of Haemoglobin and Chlorophyll.

Prostaglandins Occurrence, nomenclature, classification, biogenesis and physiological effects. Synthesis of PGE2 and PGF2α.

Pyrethroids and Rotenones Structure and reactions. 44

Books Suggested: 1. Natural Products: Chemistry and Biological Significance, J. Mann, R.S. Davidson, J.B. Hobbs, D.V. Banthrope and J.B. Harborne, Longman, Essex. 2. Organic Chemistry, Vol. 2 I.L. Finar, ELBS. 3. Stereoselective Synthesis: A Practical Approach, M. Nogradi, VCH. 4. Rodd’s Chemistry of Carbon Compounds, Ed. S. Coffey, Elsevier. 5. Chemistry, Biological and Pharmacological Properties of Medicinal Plants from the Americas, Ed. Kurt Hostettmann, M.P. Gupta and A. Marston, Harwood Academic Publishers. 6. Introduction to Flavonoids, B.A. Bohm, Hardwood Academic Publishers. 7. New Trends in Natural Product Chemistry, Atta-ur-Rahman and M.I. Choudhary, Harwood Academic Publishers. 8. Insecticides of Natural Origin, Sukh Dev, Harwood Academic Publishers.

ELECTIVE PAPER 12

CH-624

ELECTROCHEMISTRY : FUNDAMENTALS AND APPLICATIONS

UNIT I Electrode Process and their Nature Electrochemical and chemical reversibility. Equation for diffusion controlled electrode process. Log plot analysis. Understanding and diagnostic criteria for kinetically and catalytically controlled electrode processes. Adsorption and other surface phenomena coupled to electrochemical reaction.

UNIT II

Voltammetry

Potential sweep techniques. Cyclic Voltammetry: Theory, Technique and Application. Characterization of electrode reversibility. Chemically Modified Electrodes.

UNIT III

45

Pulse Polarography

Principle of pulse voltammetry, analytical usefulness. Electrochemical stripping analysis : theory, technique and applications; Adsoptive strippling voltammetry: theortical background, applications and limitations. Mercury Thin Film Electrode (M.T.F.E. ).

UNIT IV Square wave voltammetry: theory and application. Theory and application of Coulometry, Chronopotentiometry and Chronoamperometry. Introduction to Photoelectrochemistry and Spectroelectrochemistry. UNIT V Voltammetry with forced convection: Rotated disc electrode, Rotated Ring disc electrode, Stationary electrode in flowing solutions. Introduction to Sensor technology: Classification of sensor and their working. Books: 1. Modern Polarographic methods in Analytical Chemistry by A.M. Bond ( Marcel Dekker) 2. Laboratory Technique in Electroanalytical Chemistry by P.T. Kissinger and H.R. Heinaman (Marcel Dakker) 3. Electrochemical Methods : Fundamentals and Applications by A.J. Bard and L.R. Faulkner. 4. Topics in Electroanalytical Chemistry by R.C. Kapoor (AMVO Publishing Company). 5. Principles of Polarography by R.C. Kapoor and B.S. Aggarwal (Wiley Eastern Ltd.) 6. Chemical Sensors, R.W. Cattrall (Oxford University Press).


Nuclear and Radiochemistry

UNIT I Stability of the nucleus, Mass Energy relationship for nuclear reactions, Properties of nucleus, Nuclear Models (The shell model, the liquid drop model, the fermi gas model, the collective model and the optical model). UNIT II 46

Nuclear reactions, Energetics of nuclear reactions, fission and fusion reactions, spallation, fragmentation, stripping and pick up reactions, photonuclear and thermonuclear reactions. UNIT III Interaction of radiation with matter, passage of neutrons through matter, interaction of radiation with matter; measurement of radiations. UNIT IV Radiolysis of water, counting techniques (GM Ionisation, proportional and scintillation counter), counting statistics. UNIT V

Applications of radioactivity, Activation Analysis, isotopic dilution analysis, radiometric titrations, application in chemical investigations and synthesis in physiochemical analysis, in age determination and in prospecting of natural reasources. Medical agricultural and industrial applications, source of electivity. Radiation hazards and protection. Books Recommended: 1. 2. 3. 4.

Essentials of Nuclear Chemistry, H.J. Arnikar. Introduction to Nuclear Science, M.W. Sarton, East West Edition. Theory of Nuclear Structure, M.K. Pal, East West Edition. Principles of Radiochemistry, G.W.A. Newton and V.J. Robinson, Macmilan Education Ltd. 5. Nuclear Chemistry, A. Vertes and I. Kiss. 6. Source book of Atomic Energy, Glasstone, East West Edition.

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Medicinal Chemistry

UNIT I Drug design & Pharmacodynamics Development of new drugs, Procedure followed in drug design, Concepts of lead compound and lead modification, concepts of pro drugs & soft drugs, structureactivity relationship(SAR),factors affecting bioactivity, resonance, inductive effect, isosterism, bio-isosterism , Theories of drug activity : occupancy theory, rate theory, induced fit theory . An Introduction of pharmacodynamics, Mechanism of drug action, elementary treatment of enzyme stimulation, enzyme inhibition, sulphonamides , drug metabolism .

UNIT II Antineoplastic agents : Inroduction, cancer chemotherapy, special problems, role of alkylating agents and antimetabolites in treatment of cancer.Mention of carcinolytic antibiotics and mitotic inhibitors. Synthesis of cyclophosphamide , Uracil and mustards . UNIT III Cardiovascular Drugs : Intoduction , Cardiovascular diseases, drug inhibitors of peripheral sympathetic function , central intervention of cardiovascular output. Synthesis of amylnitrite, sorbitrate, atenolol.

UNIT IV Drugs: Psychotic and Antipsychotic – Inroduction, , CNS depressants, general anaesthetics, mode of action; hypnotics, sedatives, anti-anxiety drugs. Anti depressants, stereochemical aspects of psychotropic drugs. Synthesis of diazepam, alprazolam and barbiturates..

48

UNIT V Antibiotics : Cell wall biosynthesis , inhibitors , β-lactam rings , antibiotics inhibiting protein synthesis , synthesis of penicillin –G , penicillin – V, Ampicillin,Chloramphenicol and Tetracyclin. Books Suggested: 1. Introduction to Medicinal Chemistry, A. Gringuage, Wiley-VCH. 2. Wilson and Gisvold’s Text Book of Organic Medicinal and Pharmaceutical Chemistry, Ed. Robert F. Dorge. 3. An Introduction to Drug Design, S.S. Pandeya and J.R. Dimmock, New Age International. 4. Burger’s Medicinal Chemistry and Drug Discovery, Vol-1 (Chapter-9 and Ch14), Ed. M.E. Wolff, John Wiley. 5. Goodman and Gilman’s Pharmacological Basis of Therapeutics, McGraw-Hill. 6. The Organic Chemistry of Drug Design and Drug Action, R.B. Silverman, Academic Press. 7. Strategies for Organic Drug Synthesis and Design, D. Lednicer, John Wiley.


Physical Organic Chemistry

UNIT I

Principles of Reactivity Mechanistic significance of entropy, enthalpy and Gibb’s free energy. Arrhenius equation. Transition state theory. Uses of activation parameters, Hammond’s postulate. Bell-Evans-Polanyi principle. Potential energy surface model. Marcus theory of electron transfer. Reactivity and selectivity principles.

UNIT II

Kinetic Isotope Effect and Structural Effects: Theory of isotope effects. Primary and secondary kinetic isotope effects. Heavy atom isotope effects. Tunneling effect. Solvent effects. Linear free energy relationships (LFER). The Hammett equation, substituent constants, theories of substituent effects. Interpreation of σ-values. Reaction constant ρ. Deviations from Hammett equation. Dual-parameter correlations, inductive substituent constant. The Taft model, σ1- and σR-scales. 49

UNIT III

Solvation and Solvent Effects Qualitative understanding of solvent-solute effects on reactivity. Thermodynamic measure of solvation. Effects of solvation on reaction rates and equilibria. Various empirical indexes of solvation based on physical properties, solventsensitive reaction rates, spectroscopic properties and scales for specific solvation. Use of solvation scales in mechanistic studies. Solvent effects from the curvecrossing model.

UNIT IV

Steric and Conformational Properties Various type of steric strain and their influence on reactivity. Steric acceleration. Molecularmeasurements of steric effects upon rates. Steric LFER. Conformational barrier to bond rotation-spectroscopic detection of individual conformers. Acyclic and monocyclic systems. Rotation around partial double bonds. Winstein-Holness and Curtin-Hammett principle.

UNIT V Nucleophilic and Electrophilic Reactivity Structural and electronic effects on SN1 and SN2 reactivity. Solvent effects. Kinetic isotope effects. Intramolecular assisgtance. Electron trlansfer nature of SN2 reaction. Nucleophilicity and SN2 reactivity based on curvecrossing model. Relationship between polar and electron transfer reactions. SRN1 mechanism. Electrophilic reactivity, general mechanism. Kinetic of SE2-Ar reaction. Structural effects on rates and selectivity. Curve-crossing approach to electrophilic reactivity.

Books Suggested: 1. Molecular Mechanics, U. Burkert and N.L. Allinger, ACS Monograph 177, 1982. 2. Organic Chemists’ Book of Orbitals. L. Salem and W.L. Jorgenses, Academic Press. 3. Mechanism and Theory in Organic Chemistry, T.H. Lowry and K.C. Richardson, Harper and Row. 4. Introduction to Theoretical Organic Chemistry and Molecular, Modeling, W.B. Smith, VCH, Weinheim. 5. Physical Organic Chemistry, N.S. Isaacs, ELBS/Longman. 50

6. Supramolecular Chemistry, Concepts and Perspectives, J.M. Lehn, VCH. 7. The Physical Basis of Organic Chemistry, H. Maskill, Oxford University Press.


Chemistry of Materials

UNIT I Multiphase Materials Classification and properties of materials, Types of phase diagrams, Isomorphous, Eutectic, Peritectic, Monotectic and Eutectiod systems, Calculation of phase amounts from a phase diagram, Phase rule, Ferrous alloys Fe-C phase diagram, Non Ferro alloys, Phase diagrams of brass and tin bronze. UNIT II Ceramic Materials Raw materials of glass, Cement and Ceramics, Refractories, Characterization, Properties and Applications, Abrasives, kinds and uses, Powder metallurgy, Manufacturing process, Properties and Applications, Advantages and Limitations. UNIT III Composite Materials Traditional composites, concrete, Asphalt and Wood, Synthetic composites, dispersion reinforced, Particle reinforced, Laminated and fiber reinforced composites, applications of composites. UNIT IV Polymeric and advanced materials : Brief idea of following : Insulating material, Semiconductors, Superconductors, Fullerenes, Optical fibers, Organic electronic material. UNIT V Environmental effects of Materials : Corrosion mechanisms of dry and wet corrosion, Galvanic and concentration cell corrosion, Pitting and stress corrosion, Corrosion control methods, Types, preparation and uses of adhesives, Types and Application of paints and Pigments.

51

Books Suggested: 1. 2. 3. 4.

Solid State Physics, N.W. Ashcroft and N.D. Mermin, Saunders College. Material Science and Engineering, An Introduction, W.D. Callister, Wiley. Principles of the Solid State, H.V. Keer, Wiley Eastern. Materials Science, J.C. Anderson, K.D. Leaver, J.M. Alexander and R.D. Rawlings, ELBS. 5. Thermotropic Liquid Crystals, Ed., G.W. Gray, John Wiley. 6. Handbook of Liquid Crystals, Kelker and Hatz, Chemie Verlag.

Laboratory Courses CH 513 : Organic Chemistry – Lab. Course III I. Qualitative Analysis Separation, purification and identification of three components of a mixture of organic compounds (three solids or two liquids and one solid, two solids and one liquid).

II. Multi-step Synthesis of Organic Compounds Benzophenone → Benzpinacol → Benzpinacolone → Benzophenone → Benzophenone oxime → Benzanilide Benzoin → Benzil → Benzilic acid Skraup synthesis: Preparation of quinoline from aniline. Synthesis using microwaves To carry out oxidation of alcohols and oxime by PCC. Synthesis using phase transfer catalyst Alkylation of diethyl malonate or ethyl acetoacetate with an alkyl halide.

III. Extraction of Organic Cmpounds from Natural Sources 1. 2.

Isolation of cafeeine from tea leaves. Isolation of casein from milk (the students are required to try some typical colour reactions of proteins). 52

3.

Isolation of lactose from milk (purity of sugar should be checked by TLC and PC and Rfvalue reported). Isolation of piperine from black pepper. Isolation of lycopene from tomatoes. Isolation of -cartoene from carrots. Isolation of eugenol from cloves.

4. 5. 6. 7.

IV. Paper Chromatography / TLC Separation and identification of the sugars present in the given mixture of glucose, fructose and sucrose by paper chromatography and determination of Rf values. V. Spectroscopy Identification of organic compounds by the analysis of their spectral data 9(UV, IR, PMR, Ms). Spectrophotometric (UV/VIS) Estimations 1. Amino acids 2. Proteins 3. Carbohydrates 4. Ascorbic acid 5. Aspirin 6. Caffiene Books Suggested 1. Systematic Qualitative Organic analysis by H. Middleton. 2. Qualitative and Quantitative hand book of Organic analysis by H. Clark 3. Vogel’s Text book of practical Organic Chemistry by Vogel 4. Practical Organic Chemistry by N.K. Vishnoi.

CH 514 Physical Chemistry : Lab. Course IV I. Chemical Kinetics (i) To investigate the kinetics of the reaction between I- and persulphate ion (a) Order of the reaction (b) Energy of activation of the reaction. (c) Effect of ionic strength on rate. (ii)

To find out the order of the reaction of saponification of ester using unequal concentrations of reactants. II. Chemical kinetics (i) To investigate the kinetics of the reaction between ceric ammonium sulfate and glycollic acid. (a) Order with respect to ceric ion. 53

(b) Order with respect to glycollic acid. (c) Energy of activation of the reaction. (d) Effect of ionic strength on rate.

(ii)To study the reaction between cericammonium nitrate and primary alcohol.

II. Thermodynamics (i)

Determination of partial molar volume of solute (e.g.,KCl) and solvent in a binary mixture. Determination of the temperature dependence of the solubility of a compound in two solvents having similar intermolecular interactions (benzoic acid in water and in DMSO-water mixture) and calculate the partial molar heat of solution.

(ii)

III. Phase Equilibrium (i)

To find out the equilibrium constant for the triiodide formation:

(ii)

To find the formula of complex cuprammonium ion by distribution method.

IV. Conductometry (i) (ii) (iii) (iv) (v) (vi)

(vii)

To find out the equivalent conductance of strong electrolytes at different dilutions and to verify Debye Huckel Onsagar equation. To determine the equivalent conductance of a weak electrolyte at infinite dilution. To determine the dissociation constant of acetic acid/Oxalic acid and verify the Ostwald’s dilution law. To determine the degree of hydrolysis and hydrolysis constant of ammonium chloride at room temperature. To determine the activity coefficient of zinc ions in the solution of 0.002 M ZnSO4 using Debye-Huckel’s Limiting Law. Determination of the velocity constant, order of the reaction and energy of activation for saponification of ethyl acetate by NaOH conductometrically. To determine the solubility and solubility product of sparingly soluble salt (PbSO4 , BaSO4 )

V. Potentiometry/pHmetry (i) (ii)

To determine the dissociation constants of weak acids (oxalic, tartaric, phosphoric) using pH meter. To determine the temperature dependence of emf of a cell.

54

(iii)

(iv) (v)

To determine the degree of hydrolysis of aniline hydrochloride for three different solutions at room temperature and hence calculate the hydrolysis constant of the salt and dissociation constant of the base. To study the acid-base titration in a non-aqueous media using a pH meter. To find out thermodynamic constants ∆G, ∆S and ∆H for the reaction by emf measurements. Zn + H2 SO4 → Zn SO4 + H2

Books suggested: 1. Practical Physical Chemistry, A.M. James and F.E. Prichard, Longman. 2. Findley’s Practical Physical Chemistry, B.P. Levitt, Longman. 3. Experimental Physical Chemistry, R.C. Das and B. Behera, Tata McGraw Hill. 4. Advanced Practical Physical Chemistry, J.B. Yadav, Goel Publishing House. 5. Advanced Experimental Chemistry, vol.1 – Physical J.N. Gurtu and R. Kapoor, S. Chand & Co.

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